Making of a photographic image

ABSTRACT

A method for forming a photographic image which comprises treating a gelatinous silver halide photographic material in the presence of an aldehyde-type hardening agent and a compound represented by the following general formula:   WHEREIN R1 and R2 are each hydrogen, chlorine, bromine, hydroxyl group, carboxyl group, carboxyl group substituted with sodium, potassium or ammonium, sulfoxyl group, or sulfoxyl group substituted with sodium, potassium or ammonium, wherein at least one of said R1 and R2 being a carboxyl group, substituted carboxylate, sulfoxyl group or substituted sulfoxylate, and R3 and R4 each being hydrogen, an alkyl group, or a hydrocarbon ring, and product so obtained is disclosed.

Feb. 27, 1973 MAKING OF A PHOTOGRAPHIC IMAGE Inventors: Tadao Hatano; Hikoharu Hara;

Primary Examiner-J. Travis Brown Assistant ExaminerM. F. Kelley Attorney-Sughrue, Rothwell, Mion, Zinn and Mac- Masatoshi Sugiyama; Reiichi our, all Peak of Ashigara-Kamigun, Kanagawa, [57] ABSTRACT Japan A method for forming a photographic image which [73] Asslgnee' Phom Kanagawa comprises treating a gelatinous silver halide photo- Japan graphic material in the presence of an aldehyde-type [22] Fil d; O t, 19, 1970 hardening agent and a compound represented by the f ll lf 1 pp N0: 82,032 0 owmg genera ormu a B2 N R1 [30] Foreign Application Priority Data B Oct. 17, 1969 Japan ..44/83032 N [52] US. Cl ..96/50 R, 96/50 PT, 96/66 R,

96/109 wherein R and R are each hydrogen, chlorine, [51] Int. Cl ..G03c 5/26,G03c 5/30, G03c 1/34 b mi hydroxyl group, carboxyl group, carboxyl [58] Field of Search ..96/66.5, 109, 61, 50, 66 group substituted with sodium, potassium ium, sulfoxyl group, or sulfoxyl group substituted with References Cited sodium, potassium or ammonium, wherein at least one UNITED STATES PATENTS of said R and R being a carboxyl group, substituted carboxylate, sulfoxyl group or substituted sulfoxylate, 2,403,927 7/1946 Kendall et al. ..96/109 and R and R each being hydrogen, an alkyl group, or 2,282,005 5/1942 Sheppard et a1 ....96/l09 a hydrocarbon ring, and product so obtained is dis- 3,396,023 8/1968 Rees et al. ....96/l09 losed, 3,403,025 9/1968 Rees et al. ....96/l01 3,574,621 4/1971 Schaller et al ..96/66.5 23 Claims, 1 Drawing Figure DENSITY DEVELOPER F 20C 4 MINUTES DEVELOPER G I 40c 2o MQOTES I DEVELOPER H 40c/25mmurrs LOG. EXPOSURE PATENTEBFEBZTIUYS 3 718,469

DENSITY DEVELOPER F 20C 4 MINUTES DEVELOPER G 40C/ 20 MINUTES DEVELOPER H 40 C/25 MINUTES L LOG EXPOSURE INVENTORS TADAO HATANO HIKOHARU HARA MAKING OF A PHOTOGRAPHIC IMAGE BACKGROUND OF THE INVENTION The present invention relates to a method for making a photographic image and more particularly, it is con- 5 and 2 is a r y lfoxyl, carboxylate 0r sulfoxycerned with a method for making a photographic image using a compound capable of preventing fog caused by aldehyde compounds employed in the hardening of the gelatin layer.

A high temperature development process has been known as an effective method of accelerating the development rate of silver halide photographic light sensitive materials.

But in order to process a light-sensitive material at high temperature, it is necessary to prevent the emulsion layer from losing physical strength due to exces sive swelling during the treatment. Therefore, some effort must be made to raise or retain the physical strength of an emulsion layer before the development step or at least during processing. One of the methods used to date is a prehardening step prior to development, with aldehyde compounds as the hardening agents followed by removing or deactivating the unreacted aldehyde remaining in the emulsion layer by washing or by intermediate treatment. Another method is to add a hardening agent to the developer.

However, these methods encounter a disadvantage in that an increase in fog occurs at increased temperatures, although the elevated temperature shortens the time needed for processing. This disadvantage is due to the presence of aldehyde compounds as hardening agents. For example, a substantial fog occurs when a black-and-white film or color film is developedwith a developer containing an aldehyde, and in particular, an aliphatic dialdehyde. This tendency is enhanced with an increase in temperature during development. The fog which results from these aldehydes can be prevented by the use of a strong fog inhibitor such as a benzotriazole or mercaptobenzotriazole, but the sensitivity is reduced to a large extent because image development is also strongly suppressed. Furthermore, the shape of characteristic curves are often distorted resulting in a curve with a two-step gamma.

SUMMARYEFTHEiNVENTroN It is, therefore, the primary object of the present invention to provide an improved method for high temperature rapid processing which shows neither deterioration of the physical properties of an emulsion layer, nor any substantial increase in fog nor any reduction of developing speed by employing an aldehyde hardening agent together with effective anti-foggants for the aldehyde.

The present inventors have discovered that the above mentioned object can be achieved by incorporating together with an aldehyde hardening agent a compound of the formula set forth below in a developer or in a prehardening solution:

late radical and R and R are each hydrogen, an alkyl radical or form a hydrocarbon condensed ring therewith.

Examples of the compounds of the present invention are set forth below:

Compound 1.. N M.P. 380 (decomp),

SOQNE S. Maflei, Gass cliim. I ital, so, 651 (1950 V Compound 2-- CO 0H M.P. 239 (decornp.).

Compound 3 V N in U M.P. 290 (decomp),

\ O O OH Y. Kidani, Pharm. Bull.

(Japan), 7, 88 (1959).

Compound- H 7 Mil. 275, F. Ullmann,

, R. Heisler, Chem. Ber. l 42, 4263 (1909). w/ j/W N C O OH Compound 5. MP. 218 (decomp.).

T w S OsH- i Compound 6. M.P. 300 (deeomp.),

l lglliirggn, J61, C. C.

u er rg. ienL, j 27, 4092 (1962). yv l C O OH It has been disclosed in French Patent 1,491,636 that chemical fog due to a polyester substrate in a light-sensitive emulsion or due to a hardening agent added to an emulsion before coating can be removed by incorporating in a light-sensitive material, a phenazine substituted with an amino, hydroxyl, alkyl, aryl, aryloxy, arylamino or acylamino group. These compounds are similar to the compounds of the present invention but cannot produce a sufficiently strong effect as the compounds contemplated for use herein can when added to a developer or prehardener. This is primarily due to their poor solubility therein. In contradistinction, the compounds of the present invention are characterized by substitution of carboxyl or sulfoxyl groups on the phenazine ring whereby solubility of the compounds is so improved as to sufficiently increase effectiveness.

An additional advantage of the present invention is that it is not necessary to add to the light-sensitive material a compound capable of suppressing fog due to an aldehyde hardening agent because the compounds of the present invention are capable themselves of suppressing aldehyde fog effectively in a processing solution, and consequently the deterioration of the lightsensitive material during storage is prevented.

DETAILED DESCRIPTION OF THE INVENTION The compounds of the present invention are used in a developer together with an aldehyde hardening agent but in another method they may be used in a prehardening solution containing a hardening agent of the aldehyde type.

The preferred concentration of the compounds of the present invention in a developer or prehardener containing an aldehyde hardening agent varies within a range of from 20-800 mg, and most preferably, l300 mg per liter of solution, although the quantity of aldehyde present is also a factor.

The aldehyde hardening agent of the present invention is a compound having at least one aldehyde group or aldehyde releasing group such as formaldehyde, dimethylolurea, glyoxal or glutaraldehyde, or its sulfite or bisulfite adduct. In addition to the compounds of the present invention, the developer used in the invention is preferably an aqueous alkali solution containing N- methyl-p-aminophenol sulfate, dihydroxybenzene, 1- phenyl-3 pyrazolidone, phenylenediamine or their derivatives as a developing agent. The developer may further contain various preservatives such as sulfite, alkaline agents such as borax, sodium carbonate, sodium phosphate or caustic soda, hardening agents.

The prehardener used in the present invention prior to development may contain, in addition to hardening agents and compounds of the invention, various inorganic salts such as sodium sulfate or magnesium sulfate as well as pH-controlling substances such as borax, sodium phosphate, acetic acid or boric acid.

As illustrated above, the important feature of the compounds of the present invention resides in their use in a processing solution, but as an alternate method, they may have been incorporated previously in an emulsion (as opposed to a processing solution) so as to prevent fog resulting from the use of aldehyde. When a photographic material obtained by adding a compound of the present invention to an emulsion in a proportion of 40-400 mg per 1 g-mole of silver halide before coating, is treated with a hardening developer or prehardener containing an aldehyde hardening agent, fog can be maintained at a low level. The prehardener or hardening developer in this case is the same as illustrated above, but free from a compound of the present invention.

The present invention is applicable to the processing of light-sensitive materials having a gelation-silver halide emulsion and in particular, for the high temperature rapid treatment of black-and-white and color lightsensitive materials.

A better understanding of the present invention will be attained from the following examples which are merely intended to be illustrative and not [imitative of the present invention. All parts are by weight unless otherwise stated.

EXAMPLE 1 An X-ray film subjected to sensitometric exposure using a standard sensitometer was subjected to a high temperature rapid processing of the following procedures.

Development Temperature Time 1. Development 39C 40 sec 2. Fixing 35C 5 min 3. Washing 20C 10 min Developer A l-phenyl-B-pyrazolidone 1.5 g hydroquinone 20 g anhydrous sodium sulfite 50 g caustic soda 20 g EDTA (2Na) 3 g S-methyl-benzotriazole 0.200 g potassium bromide 0.8 g water to make 1 liter Developer B Twelve ml (by volume of 25 percent glutaraldehyde was added to 1 liter of Developer A.

Developer C Twelve ml (by volume) of 25 percent glutaraldehyde and 0.144 g of Compound 2 were added to 1 liter of Developer A.

Developer D Twelve ml (by volume) of 25 percent glutaraldehyde and 0.144 g of Compound 3 were added to 1 liter of Developer A.

Developer E Twelve ml (by volume) of 25 percent glutaraldehyde and 0.177 g of Compound 4 were added to 1 liter of Developer A.

The fixing solution used was a conventional fixing solution containing sodium thiosulfate as a solvent for the silver halide.

The results of photographic characteristics thus obtained are shown in the following table. As is evident from these results, in the films passed through Developers C, D and E, fog resulting from the use of an aldehyde can effectively be prevented without any par ticular reduction of the sensitivity and gamma. As also predicted, the physical strength of the emulsion layer is kept sufficiently high during the processing.

Developer Relative Sensitivity Gamma Fog (Fog l) A I00 [.95 0.32 B 1.40 0.68 c as 2.00 0.33 D 78 2.30 0.32 E 101 1.75 0.30

EXAMPLE 2 The same X-ray film as that of Example 1 was exposed and developed as follows using three developers.

1. Developed at 20C for 4 minutes using Developer F (Rendol* mono-methyl-p-amino phenol 4.0

NaSO 60.0 hydroquinone 10.0 Na,C0 53.0

KBr Water to make a commercial developer for X-ray film).

2. Developed at 40C for 20 minutes using Developer G (prepared by adding 12 ml (by volume) of 25 percent glutaraldehyde to 1 liter of Developer A OF Example l 3. Developed at 40C for 25 minutes using Developer H (prepared by adding 12 ml (by volume) of 25 percent glutaraldehyde and 200 g of Compound 5 to 1 liter of Developer A of Example (1).

The results obtained are shown in the drawing accompanying this specification. As is evident therefrom, when the development is carried out at a high temperature according to the present invention, the photographic characteristics are close to those exhibited by the conventional developer (F) and the time of development is shortened to about one-tenth.

EXAMPLE 3 A commercial high speed negative film was subjected to sensitometric exposure by means of sensitometer and then developed at 20C for 7 minutes using the following four developers.

2.5 1 liter Developer l l-phenyl-Zl-pyrazolidone g hydroquinone 5.0 g anhydrous sodium sulfite 50 g sodium carbonate (monohydrate) 25 g potassium bromide 2 0 g water to make 1 ing development.

Developer l 0.33 Developer J l.07 Developer K 0.33 Developer L 0.63

EXAMPLE 4 A color development procedure in which color formers are incorporated in a color developer (so called coupler developer) normally requires fairly long processing time since it consists of many complicated steps.

Accordingly, it is important to keep the physical strength of the emulsion layer sufficient throughout the process. For this purpose a prehardening treatment prior to development is ordinarily employed to raise the physical strength of the emulsion layer.

Time

Process l Temperature 1. Prehardening 27C 1 minute 2. Washing 27C 1 minute 3. First development 27C 5 minute 4. Washing 27C 2 minute 5. Red reversal exposure 6. Cyan development 27C 5 minute 7. Washing 27C 1 minute 8. Violet reversal exposure 9. Yellow development 27C 5 minute 10. Washing 27C l minute 11. Auxiliary development 27C l minute 12. Washing 27C 1 minute 13. Magenta development 27C 5 minute [4. Washing 27C 1 minute 15. Bleaching 27C 2 minute 16. Fixing 27C 2 minute 17. Washing 27C 2 minute 18. Drying If in order to shorten this process the prehardening and subsequent water washing steps are omitted and instead, a hardening agent is added to the first developer, the physical strength of the emulsion layer is main tained but the color density diminishes remarkably, resulting in deterioration of the image quality. However, incorporating a compound of the present invention with a hardening agent of the aldehyde type can suppress efi'ectively the formation of fog in the first development, so that the simplification and shortening of the process steps may be performed without deteriorating the color image quality.

Accordingly, in the present invention, the prehardening and water washing steps prior to the first development may be omitted. As an added feature, the time for the first development is shortened because of elevated temperature. One example for the improved process is as follows:

Process Temperature Time 1. First development 40C seconds (hardening development) 2. Water washing 40C 30 seconds The other steps from the red reversal exposure to drying are similar to those of Process 1.

Commercial reversal color light-sensitive materials of the coupler-in-developer type are subjected to sensitometric exposure by means of a sensitometer and one of the materials is passed through Process I while the other is passed through Process Il. The results are shown in the following table. As is evident from these results, in the improved process wherein the compound of the invention is used, substantially similar photographic characteristics to those of Process 1 are obtained.

Process- First Relative Maximum ing developer Sensitivity Sensitivity R G B R (i B l formula M I00 I00 3.83 3.00 320 ll formula N 98 103 105 3.70 2.40 2.75 "(improcompound 3 98 97 100 3.80 3.05 3. l 5 ved) is added to formula N in a ratio of 144 mg] liter Composition of the prehardener in Process 1 sodium hexametaphosphate 2 g sodium bisulfite 2 g sodium pyrophosphate l0 hydrate 30 g sodium sulfate g formalin (37% aqueous solution) 18 ml (by volume potassium bromide 2.5 g caustic soda 0.] g water to make 1 liter First developer formula M M-methyl-p-aminophenol sulfate 2.0 g anhydrous sodium sulfite 90 g hydroquinone sodium carbonate (monohydrate) 1.0 g 1 liter potassium thiocyanate water to make First developer formula N Fifteen ml (by volume) of 37 percent aqueous solution of formaldehyde is added to 1 liter of the formula M.

Cyan color developer anhydrous sodium sulfite 4-amino-3-methyl-N,N diethylaniline hydrochloride sodium carbonate (monohydrate potassium bromide potassium iodide (0.1% aqueous solution l,5-dihydroxy-2,6-dibromonaphthalene caustic soda water to make by volume EON roman Yellow color forming developer anhydrous sodium sulfite 4 amino-N,N-diethylaniline hydrochloride potassium bromide potassium iodide (0.1% aqueous solution 3-benzolyl-4-(ptoluenesulfonamide) acetanilide caustic soda water to make min 1. g l(by volume) l iter Magenta color forming developer anhydrous sodium sulfite 4-amino-3-methyl-N,N- diethylaniline sulfate EXAMPLE 5 A silver iodobromide-gelatin emulsion (silver iodide 5 mol percent) was coated onto a film support of cellulose acetate in a proportion of 60 mg of silver halide and 75 mg of gelatin per dm to prepare a photographic material for X-ray. To this emulsion was added a compound of the present invention before coating as shown in the table.

Each sample was exposed by an X-ray of 80 KV and developed at 37C for 60 seconds with Developer B of Example 1.

The results demonstrate that the compounds of the present invention are effective when added previously to the emulsion also.

Compound added Fog No 0.80 Compound 1 220 mg/g-mole 0.32 silver halide Compound 4 300 mg/g-mole 025 silver halide Compound 5 300 mg/g-mole 0.25 silver halide EXAMPLE 6 Synthesis of l-phenazinecarboxylic acid (Compound 2):

To a suspension of 68.5 g of anthranilic acid in 500 ml (by volume) of xylene, 61.5 g of nitrobenzene and 200 g of potassium hydroxide paste (prepared by pulverization of 500 g of pelletized potassium hydroxide in 500 ml. of toluene by a ball mill) were added. The resulting mixture was heated under reflux for 8 hours with stirring. The mixture was poured into 1.5 l. of water followed by a separation of the aqueous layer. The aqueous layer was neutralized with acetic acid, icecooled and extracted with 2 l. of toluene. The extract was then re-extracted with l l. of 1 N sodium hydroxide solution. The alkaline extract was neutralized with acetic acid, yielding crystals, which were then extracted with 2 l. of toluene, followed by a concentration of the extract. The resulting residue was treated with a small amount of acetone to separate the crystals. The crystals were filtered and washed with a small amount of acetone, dried and recrystallized from acetic acid to give 4 g of yellow needle-like material, mp. 239C (decomp.).

EXAMPLE 7 Synthesis of 5-benzol[a]phenazinesulfonic acid (Compound 5 To a hot solution of 5 g of 2-nitroso-l-naphthol-4- sulfonic acid in 50 ml (by volume) of water were added a hot solution of 2 g of O-phenylenediarnine in 30 ml (by volume) of water and 10 ml (by volume) of 6N hydrochloric acid. The resulting solution was heated on a water bath for 10 minutes with stirring. The precipitate was filtered and recrystallized from percent acetic acid to give 5 g of yellow needle-like material, mp. 218C (decomp.).

Though the present invention has been adequately set forth in the foregoing specification and examples included therein, it is readily apparent that various changes and modifications may be made without departing from the scope thereof.

What is claimed is:

1. A method for forming a photographic image wherein an exposed gelatinous silver halide photographic material is optionally prehardened, developed, fixed or washed, which comprises contacting said exposed gelatinous silver halide photographic material with an aldehyde hardening agent and a compound represented by the following general formula:

wherein R and R are each hydrogen, chlorine, bromine, hydroxyl group, carboxyl group, carboxyl group substituted with sodium, potassium or ammonium, sulfoxyl group, or sulfoxyl group substituted with sodium, potassium or ammonium, wherein at least one of said R and R being a carboxyl group, substituted carboxylate, sulfoxyl group or substituted sulfoxylate, and R and R each being hydrogen, an alkyl group, or hydrocarbon ring.

2. The method as claimed in claim 1 wherein said compound is incorporated into a prehardening solution.

3. The method as claimed in claim 1 wherein said compound is incorporated into a developing solution.

4. The method of claim 1 wherein said compound is represented by the structure:

(300E Q U y 5. The method of claim 1 wherein said compound is represented by the structure:

6. The method of claim' 1 wherein said compound is represented by the structure:

7. The method of claim 1 wherein said compound is represented by the structure:

COOH

8. The method of claim 1 wherein said compound is represented by the structure:

9. The method of claim 1 wherein said compound is represented by the structure:

I COOH 10. A method for forming a photographic image which comprises developing an exposed gelatinous silver halide photographic material with a developer containing a developing agent, an aldehyde or aldehyde releasing agent and a compound of the formula:

Br g wherein R and R are Sci hydrogen, chlorine, bromine, hydroxyl group, carboxyl group, carboxyl group substituted with sodium, potassium or ammoniof the present invention is a member selected from the group consisting of and 13. The method of claim 10 wherein the aldehyde releasing compound is glutaric aldehyde and the compound of the present invention is:

14. The method of claim 10 wherein the aldehyde releasing compound is glutaric aldehyde and the compound of the present invention is:

15. The method of claim 1 wherein the concentration of the compound of the present invention ranges from 20 to 800 g/liter of solution.

16. The method of claim 10 wherein the concentration of the compound of the present invention ranges from 40 to 400 g/g-mole of silver halide.

17. The method of claim wherein the concentration of the compound of the present invention ranges from 100-300 g/liter of solution.

18. The method of claim 10 wherein the developing inorganic salts are selected from the group consisting of sodium sulfate and magnesium sulfate.

21. The method as claimed in claim 19 wherein said pH-controlling substances are selected from the group agent is a member selected from the group consisting of 5 consisting of borax, sodium p p acetic a id and N-methyl-p-aminophenol sulfate, dihydroxybenzene, l-phenyl-3-pyrazolidone, phenylenediamine and their derivatives.

19. The method as claimed in claim 2 wherein said pre-hardening solution also contains inorganic slats and pH-controlling substances.

20. The method according to claim 19 wherein said boric acid.

22. The method as claimed in claim 2 wherein said pre-hardening solution also contains a pl-l-controlling substance.

23. The method as claimed in claim 2 wherein said pre-hardening solution also contains an inorganic salt. 

2. The method as claimed in claim 1 wherein said compound is incorporated into a prehardening solution.
 3. The method as claimed in claim 1 wherein said compound is incorporated into a developing solution.
 4. The method of claim 1 wherein said compound is represented by the structure:
 5. The method of claim 1 wherein said compound is represented by the structure:
 6. The method of claim 1 wherein said compound is represented by the structure:
 7. The method of claim 1 wherein said compound is represented by the structure:
 8. The method of claim 1 wherein said compound is represented by the structure:
 9. The method of claim 1 wherein said compound is represented by the structure:
 10. A method for forming a photographic image which comprises developing an exposed gelatinous silver halide photographic material with a developer containing a developing agent, an aldehyde or aldehyde releasing agent and a compound of the formula:
 11. The method of claim 10 wherein the aldehyde releasing compound is selected from the group consisting of formaldehyde, glutaric aldehyde, dimethylolurea, glyoxal and its sulfite or bisulfite adduct.
 12. The method of claim 10 wherein the compound of the present invention is a member selected from the group consisting of
 13. The method of claim 10 wherein the aldehyde releasing compound is glutaric aldehyde and the compound of the present invention is:
 14. The method of claim 10 wherein the aldehyde releasing compound is glutaric aldehyde and the compound of the present invention is:
 15. The method of claim 1 wherein the concentration of the compound of the present invention ranges from 20 to 800 g/liter of solution.
 16. The method of claim 10 wherein the concentration of the compound of the present invention ranges from 40 to 400 g/g-mole of silver halide.
 17. The method of claim 15 wherein the concentration of the compound of the present invention ranges from 100-300 g/liter of solution.
 18. The method of claim 10 wherein the developing agent is a member selected from the group consisting of N-methyl-p-aminophenol sulfate, dihydroxybenzene, 1-phenyl-3-pyrazolidone, phenylenediamine and their derivatives.
 19. The method as claimed in claim 2 wherein said pre-hardening solution also contains inorganic slats and pH-controlling substances.
 20. The method according to claim 19 wherein said inorganic salts are selected from the group consisting of sodium sulfate and magnesium sulfate.
 21. The method as claimed in claim 19 wherein said pH-controlling substances are selected from the group consisting of borax, sodium phosphate, acetic acid and boric acid.
 22. The method as claimed in claim 2 wherein said pre-hardening solution also contains a pH-controlling substance.
 23. The method as claimed in claim 2 wherein said pre-hardening solution also contains an inorganic salt. 